Theoretical investigation of fluorescence changes caused by methanol bridge based on ESIPT reaction*

Abstract

The different fluorescence behavior caused by the excited state proton transfer in 3-hydroxy-4-pyridylisoquinoline (2a) compound has been theoretically investigated. Our calculation results illustrate that the 2a monomer in tetrahydrofuran solvent would not occur proton transfer spontaneously, while the 2a complex in methanol (MeOH) solvent can undergo an asynchronous excited state intramolecular proton transfer (ESIPT) process. The result was confirmed by analyzing the related structural parameters, infrared vibration spectrum and reduced density gradient isosurfaces. Moreover, the potential curves revealed that with the bridging of single MeOH molecular the energy barrier of ESIPT was modulated effectively. It was distinctly reduced to 4.80 kcal/mol in 2a-MeOH complex from 25.01 kcal/mol in 2a monomer. Accordingly, the ESIPT process induced a fluorochromic phenomenon with the assistant of proton-bridge. The elucidation of the mechanism of solvent discoloration will contribute to the design and synthesis of fluorogenic dyes as environment-sensitive probes.